I. Field of the Invention
This invention relates to new propynyl compounds, to new synergistic insecticidal compositions comprising such compounds, and to their use. More particularly, it relates to 1-(2-propynyl)-1 H-indazole compounds, synergistic insecticidal compositions comprising said compounds, and to their use.
It has been discovered that certain propynyl compounds, more fully described below, synergistically enhance the insecticidal activity of carbamate, organophosphorus and chrysanthemum mono- and di-carboxylic ester insecticides. This synergistic action is, moreover, highly selective in that the toxicity of the insecticides to warm-blooded animals is not appreciably increased.
The propynyl synergist compounds of the invention operate to protect the environment in which they are used by permitting the use of a lesser dose of insecticide to obtain a percentage insect mortality comparable to that which would result from a larger dose of insecticide alone. This is of particular importance where the insecticide is environmentally persistent or is highly toxic to birds, fish or mammals. Further, in a number of instances, these propynyl synergist compounds broaden the spectrum of activity of the insecticide. They also restore the activity of insecticides against insects which have developed resistance to the insecticide where such resistance is due to metabolism, i.e. enzymic detoxification, of the insecticide. In so restoring activity against resistant insects, it is believed that the propynyl synergist compounds act to inhibit enzymic detoxification.
The insecticidal carbamates with which the synergist compounds of this invention may be used include: 3,4-xylyl methyl carbamate; 3,4,5-trimethylphenyl methylcarbamate; 2,3,4-trimethylphenyl methylcarbamate; m-cym-5-yl-methylcarbamate; o-sec-butylphenyl methylcarbamate; m-(1-ethylpropyl) phenyl methylcarbamate; m-(1-methylbutyl) phenyl methylcarbamate; 3,4-di-t-butylphenyl methylcarbamate; o-chlorophenyl methylcarbamate; o-isopropoxyphenyl methylcarbamate [Baygon]; 4-(methylthio) 3,4-xylyl methylcarbamate; 4-dimethylamino-m-tolyl methylcarbamate; 4-dimethylamino-3,5-xylyl methylcarbamate; m-[(dimethylamino)methylene]amino phenyl methylcarbamate, hydrochloride; o-(1,3-dioxolan-2-yl) phenyl methylcarbamate; o-(4,5-dimethyl-1,3-dioxolan-2-yl) phenyl methylcarbamate; 1-naphthyl methylcarbamate [carbaryl]; 2,3-dihydro-2,2-dimethyl-7-benzofuranyl methylcarbamate; 1-(dimethylcarbamoyl)-5-methyl-3-pyrazolyl dimethylcarbamate [Dimetilan]; 3-methyl-1-phenyl-5-pyrazolyl-N-dimethylcarbamate [pyrolan]; 4-benzo(b) thienyl-N-methylcarbamate [mobam]; 8-(2-methylquinolyl)-N-methylcarbamate [GS 13798]; and 3,5-di-isopropylphenyl methylcarbamate [HRS 1422]. The preferred insecticidal carbamates are carbaryl, mobam, pyrolan, Dimetilan, Baygon, GS 13798 and HRS 1422.
The insecticidal organophosphorus compounds with which the synergist compounds of the invention may be used include: 3-hydroxy-N,N-dimethyl-cis-crotonamide, dimethyl phosphate [Bidrin]; 2-chloro-N,N-diethyl-3-hydroxycrotonamide, dimethyl phosphate; O,O-dimethyl S(4-oxo-1,2,3-benzotriazin-3 (4H)-ylmethyl) phosphorodithioate; 2-chloro-1-(2,4-dichlorophenyl) vinyl diethyl phosphate; 2-chloro-1-(2,4,5-trichlorophenyl) vinyl dimethyl phosphate [Gardona]; S-((2-methoxy-5-oxo-.DELTA..sup.2 -1,3,4-thiadiazolin-4-yl)methyl) O,O-dimethyl phosphorodithioate [GS 13005]; and O,O-diethyl O-(2-isopropyl-4-methyl-6-pyrimidyl) phosphorothioate [Diazinon]. The preferred insecticidal organophosphorus compounds are GS 13005, Diazinon, Gardona and Bidrin.
The synergist compounds of the present invention may be employed with insecticidal esters of 2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylic acid. The preferred esters are 3-(2,4-pentadienyl)-4-oxo-2-cyclopenten-1-yl chrysanthemumate, 3-(2-butenyl)-4-oxo-2-cyclopenten-1-yl-chrysanthemumate, 3-allyl-2-methyl-4-oxo-2-cyclopenten-1-yl chrysanthemumate, 6-chloropiperonyl chrysanthemumate, 2,4-dimethylbenzyl chrysanthemumate, 2,3,4,5-tetrahydrophthalimidomethyl chrysanthemumate and (5-benzyl-3-furyl) methyl chrysanthemumate. These synergist compounds may also be utilized with insecticidal esters of 2,2-dimethyl-3-(2-carbomethoxypropenyl)-cyclopropanecarboxylic acid. The preferred esters are methyl 3(2,4-pentadienyl)-4-oxo-2-cyclopenten-1-yl chrysanthemumdicarboxylate and methyl 3(2-butenyl)-4-oxo-2-cyclopenten-1-yl chrysanthemumdicarboxylate.
The propynyl synergist compounds with which the present invention is concerned are of four classes: [I] O-(2-propynyl) oximes; [II] Benzyl 2-propynyl ethers; [III] N-(2-propynyl) indazoles; and [IV] (2-propynyloxy) alkyl arenes.
The novel O-(2-propynyl) oximes of this invention are represented by the formula ##EQU1## wherein the symbol R represents hydrogen, aryl or alkyl of not more than five carbon atoms; and where R.sub.1 is (a) naphthyl, provided R is other than hydrogen, or (b) a substituted or unsubstituted aromatic hydrocarbon selected from the group consisting of ##SPC2##
wherein X and Y represent hydrogen, nitro, substituted amino, alkoxy of less than three carbon atoms, or, when R is other than hydrogen, halogen other than iodine.
Examples of these oximes are given in Table I.
TABLE I ______________________________________ Compound No. R R.sub.1 ______________________________________ I-A H (3,4-(CH.sub. 3 O).sub.2)C.sub.6 H.sub.3 -- I-B H (3-NO.sub. 2)C.sub.6 H.sub.4 -- I-C H (4-(CH.sub. 3).sub.2 N)C.sub.6 H.sub.3 -- I-D CH.sub.3 (4-Cl)C.sub. 6 H.sub.4 -- I-E CH.sub.3 C.sub.6 H.sub.5 -- I-F CH.sub.3 .beta.-C.sub. 10 H.sub.7 -- ______________________________________
As illustrated in Example 5, the oximes of formula I synergistically enhance the lethality of insecticidal carbamates.
It has been found that the lethality of insecticidal organophosphorus compounds and of the aforesaid insecticidal cyclopropanecarboxylic acid esters is synergistically enhanced by O-(2-propynyl) oximes represented by the formula ##EQU2## wherein R represents hydrogen, aryl, or alkyl of not more than five carbon atoms and R.sub.1 represents a substituted or unsubstituted aromatic hydrocarbon group selected from the class consisting of naphthyl and groups having the structure ##SPC3##
where X and Y represent hydrogen, nitro or halogen other than iodine.
Examples of these oximes are compounds I-B, I-D, I-E, I-F and the compounds of Table Ia.
TABLE Ia ______________________________________ Compound No. R R.sub.1 ______________________________________ I-G H (2,4-Cl.sub.2)C.sub.6 H.sub.3 -- I-H H (4-Cl)C.sub.6 H.sub.4 -- I-I H .alpha.-C.sub.10 H.sub.7 -- ______________________________________
The lethality of insecticidal carbamates has been found to be enhanced synergistically by benzyl 2-propynyl ethers represented by the formula ##SPC4##
wherein X, Y and Z represent hydrogen, nitro, halogen other than iodine, or, when X is hydrogen, Y and Z taken together may represent methylenedioxy, and provided that, when both X and Y are hydrogen, Z is other than nitro.
Examples of these benzyl 2-propynyl ethers are given in Table II and their synergistic activity with insecticidal carbamates is illustrated in Example 6.
TABLE II ______________________________________ Compound No. X Y Z ______________________________________ II-A H H 4-Cl II-B H 2-Cl 4-Cl II-C H 3-Cl 4-Cl II-D 2-Cl 3-Cl 4-Cl II-E 2-Cl 3-Cl 6-Cl II-F 2-Cl 4-Cl 5-Cl II-G H 3,4-CH.sub.2 O.sub.2 II-H H 2-Cl 6-Cl II-I H 2-NO.sub.2 3-Cl II-J H 2-NO.sub.2 4-Cl II-K H 2-NO.sub.2 6-Cl II-L H 3-NO.sub.2 2-Cl II-M H 3-NO.sub.2 4-Cl II-N H 4-NO.sub.2 2-Cl II-O H 4-NO.sub.2 3-Cl ______________________________________
It has been found that the lethality of insecticidal organophosphorus compounds and of the aforesaid cyclopropanecarboxylic acid esters is synergistically enhanced by benzyl 2-propynyl ethers represented by the formula EQU R--CH.sub.2 --O--CH.sub.2 --C.quadbond.CH
wherein R represents an aromatic hydrocarbon selected from the class consisting of naphthyl and groups having the structural formula ##SPC5##
wherein X, Y and Z represent hydrogen, nitro or halogen other than iodine.
Examples of these benzyl 2-propynyl ethers are compounds II-A through II-F and II-H through II-O, inclusive, and the compounds of Table IIa.
TABLE IIa ______________________________________ Compound No. R ______________________________________ II-P (2-NO.sub.2)C.sub.6 H.sub.4 -- II-Q (4-NO.sub.2)C.sub.6 H.sub.4 -- II-R .alpha.-C.sub.10 H.sub.7 -- ______________________________________
The novel N-(2-propynyl) indazoles of this invention are represented by the formula ##SPC6##
wherein R represents hydrogen or halogen other than iodine, R.sub.1 represents hydrogen or nitro, and R.sub.2 represents hydrogen, nitro or halogen other than iodine.
Examples of these indazoles are given in Table III and their synergistic activity with insecticidal carbamates is illustrated in Example 7.
TABLE III ______________________________________ Compound No. R R.sub.1 R.sub.2 ______________________________________ III-A H 5-NO.sub.2 H III-B 3-Cl H H III-C 3-Cl H 6-NO.sub.2 III-D H H 6-Cl III-E H H 6-NO.sub.2 ______________________________________
The novel (2-propynyloxy) alkyl arenes of this invention are represented by the formula ##EQU3## wherein R represents hydrogen or alkyl of not more than three carbon atoms, R.sub.1 represents nitro, chlorine or bromine, and R.sub.2 represents an aromatic hydrocarbon selected from the class consisting of naphthyl and groups having the formula ##SPC7##
wherein X and Y represent hydrogen, nitro or halogen other than iodine.
Examples of these compounds are given in Table IV and their synergistic activity with insecticidal carbamates and insecticidal organophosphorus compounds is illustrated in Examples 8 and 11, respectively.
TABLE IV ______________________________________ Compound No. R R.sub.1 R.sub.2 ______________________________________ IV-A CH.sub.3 NO.sub.2 (2,4-Cl.sub.2)C.sub.6 H.sub.3 -- IV-B CH.sub.3 NO.sub.2 .alpha.-C.sub.10 H.sub.7 -- IV-C CH.sub.3 NO.sub.2 (4-Cl)C.sub.6 H.sub.4 -- ______________________________________
The following examples illustrate the preparation of propynyl compounds within the foregoing four classes.